Triazolone herbicides

ABSTRACT

Triazolone herbicides of the formula: ##STR1## where V is hydrogen, fluorine, chlorine, bromine, methyl or OR where R is alkyl of 1-4 carbon atoms; 
     X is hydrogen, fluorine, chlorine, bromine, cyano, methyl, methoxy, or nitro; 
     Y is hydrogen, fluorine, chlorine, bromine, or methyl; 
     N, m is 0, 1, 2, 3 or 4; 
     Q is oxygen or sulfur; 
     Z is oxygen, S(O) p  or NR&#39;; 
     p is 0, 1 or 2 and 
     R&#39; is alkyl of 1-3 carbon atoms 
     With the provisos that 
     (1) n + m = 2, 3, or 4; and 
     (2) if n + m = 2 or 4 then Y, X ≠ H 
     and when Z is S(O) p , n is 1, 2, 3 or 4.

BACKGROUND OF THE INVENTION

West German Application No. 1,948,793, dated Sept. 26, 1969, discloses amethod for preparation of a broad general class of4,5,6,7-tetrahydroindazoles which are useful intermediates in thepreparation of pharmaceuticals, agricultural chemicals and corrosioninhibitors. ##STR2##

Specifically disclosed in the preparation of Compound Ib, where R₂, R₃,and R₄ are hydrogen and R₁ is phenyl, from Compound IIb (samesubstitution) by catalytic reduction.

The preparation and fungicidal utility of the2-p-chlorophenylindazol-3-one is disclosed in Takeda Chem. Ind. Paper,Chem. Abs., 67, 11542h (1967): ##STR3##

2-Aryl-4,5,6,7-tetrahydro-1-alkyl-1H-indazol-3(2H)-ones are claimed asantipyretics in Ger. Pat. No. 668,628 [assigned to P. Beierdorf & Co.AG, Chem. Abs., 33, 5131² (1939)] and U.S. Pat. No. 2,104,348 [assignedto E. R. Squibb Co., Chem. Abs., 32, 1869¹ (1938)]. ##STR4##

1-Phenyl-3,4-trimethylenepyrazolone is disclosed in U.S. Pat. No.1,685,407 (1928) with utility as intermediate for making dyes andmedicinal compounds. C. Mannich in Arch. Pharm. 267, 699-702 (1929) andin Brit. Pat. No. 260,577 describes the preparation of1-phenyl-3,4-trimethylenepyrazolones. ##STR5##

R. P. Williams et al. in J. Med. Chem. 13, 773 (1970) reports thepreparation and evaluation as anti-inflammatory agents compounds of thefollowing type: ##STR6## X ═ H, Br, F.

Although some of the compounds disclosed in the above-cited referencesare useful as agricultural products, none are taught to be outstandingherbicides. The presence of undesired vegetation is very damaging touseful crops. In the current world situation, wherein food shortages areacute, it is most important not to lose a portion of a valuable crop.The presence of such undesired vegetation results in the loss of asignificant portion of such crops. Thus, a need exists for aparticularly effective herbicide which will destroy unwanted vegetation.

According to the instant invention, such herbicidal compounds have beendiscovered.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I, to agriculturalcompositions containing them, and to the method of use of thesecompounds as general herbicides for the pre- or post-emergence controlof undesired vegetation. ##STR7## where V is hydrogen, fluorine,chlorine, bromine, methyl or OR where R is alkyl of 1-4 carbon atoms;

X is hydrogen, fluorine, chlorine, bromine, cyano, methyl, methoxy, ornitro;

Y is hydrogen, fluorine, chlorine, bromine, or methyl:

n, m is 0, 1, 2, 3 or 4;

Q is oxygen or sulfur;

Z is oxygen, S(O)_(p) or NR';

p is 0, 1 or 2 and

R' is alkyl of 1-3 carbon atoms

with the provisos that

(1) n + m = 2, 3, or 4; and

(2) if n + m = 2 or 4 then Y, X ≠ H and when Z is S(O)p, n is 1, 2, 3 or4.

Preferred for their high herbicidal activity are those compounds ofFormula I where, independently:

Q is oxygen; and

Z is oxygen, S(O)p or --NR' where R' is alkyl of 1-3 carbon atoms

p is 0, 1 or 2 and when Z is S(O)p, n is 1, 2, 3 or 4.

More preferred for their higher herbicidal activity or favorable cost orboth are those compounds of the preferred where, independently:

V is hydrogen, chlorine, bromine or OR;

X is fluorine, chlorine or bromine;

Y is flourine, chlorine, bromine, or methyl;

n + m is 3 and when Z is S(O)p, n ≠ 0.

Most preferred for their excellent herbicidal activity or more favorablecost or both are those compounds of the more preferred where,independently:

V is hydrogen, chlorine or OR;

X is chlorine or bromine; and

Y is fluorine, chlorine or bromine.

Specifically preferred for their outstanding herbicidal activity orhighly favorable cost or both are

2-[2,4-dichloro-5-(1-methyethoxy)phenyl]-6,7-dihydro-5H-1,2,4-triazolo[3,4-B][1,3]-oxazin-3-(2H)-one,m.p. 179.5°-180.5°;

2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-5,6,7,8-tetrahydro-8-methyl-1,2,4-triazolo[4,3-A]pyrimidin-3(2H)-one,oil;

2-(2,4-dichloro-5-methoxyphenyl)-6,7-dihydro-5H-1,2,4-triazolo[3,4-B][1,3-oxazin-3(2H)-one,m.p. 122°-123.5°;

2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-2,5,6,8-tetrahydro-3H-1,2,4-triazolo[3,4-C][1,4]oxazin-3-one,oil.

SYNTHESIS OF THE COMPOUNDS

The compounds of Formula I where Z is oxygen (Formula Ia) are preparedas shown in equations A and B. The imino ethers l where K can ##STR8##be oxygen or sulfur and R" is a lower alkyl group (C₁ -C₈) especiallymethyl or ethyl are prepared by methods known in the art. For example,3-methoxy-5,6-dihydro-2H-oxazine 5 can be prepared according toprocedures taught in ##STR9## Chem.Ber.101,1979 (1968).2-Methylthio-5,6-dihydro-4H-1,3-oxazine 6 can be prepared according tomethods disclosed in Can. J. Chem. 5,107 (1968).3-Ethoxy-5,6-dihydro-4H-1,2-oxazine 7 can be prepared according toprocedures taught in Izv. Akad. Nauk. SSSR, Otd. Khim. Nauk 1074 (1962),all of which are herein incorporated by reference.

The amidrazone acid salts, e.g., hydrochlorides 3 may be preparedaccording to methods taught in Belgium Pat. Nos. 802,446 and 802,447.The conversion of the amidrazones or their acid salts (e.g.hydrochlorides) 3, to the compounds of Formula Ia is accomplished byreaction with either phosgene (Q in Formula 4 is oxygen) which yieldsthe compounds of Formula Ia wherein Q is oxygen, or thiophosgene (Q inFormula 4 is sulfur) which yields the compounds of Formula Ia wherein Qis sulfur. The reaction is run in a suitable inert organic solvent, e.g.an aromatic hydrocarbon such as benzene or toluene, a chlorinated alkanesuch as chloroform or methylene chloride, or an ether-type solvent suchas tetrahydrofuran. In order to neutralize the acid liberated during thereaction, a suitable base is used, such as a tertiary amine, e.g.pyridine or triethylamine. Ordinary precautions are taken to excludemoisture from the reaction. For completion of the reaction, it issometimes necessary to heat the reaction mixture to reflux for a periodof one to 24 hours. The product of the reaction is isolated by pouringthe reaction mixture into water and extracting the product with asuitable solvent, e.g. ether or methylene chloride. The organic extractof the product is dried by addition of a drying agent, e.g. anhydroussodium sulfate, and the solvent is removed by distillation orevaporation at reduced pressure, leaving the crude product. Purificationof the crude material is accomplished by standard techniques, e.g.crystallization, chromatography or distillation.

Many of the compounds of Formula Ia, wherein Q is oxygen, can also beprepared in two steps as shown in Equation c. ##STR10## wherein R''' isan alkyl group of 1 to 3 carbon atoms. The amidrazone acid salt 3 in asuitable solvent, e.g. anhydrous tetrahydrofuran, can be reacted withthree equivalents of n-butyllithium 8 which generate the amidrazonedianion 9. If the amidrazone free base is used, only two equivalents ofn-butyllithium are necessary to generate the dianion 9. Otherwise, ineach of the reactions according to Equation c, the same conditions canbe used. The reaction temperature is maintained between -10° and 10° C.After the addition of n-butyllithium is completed, the reaction isstirred for a brief period (e.g. between 5 and 30 minutes) whilemaintaining the temperature. One equivalent of an alkyl chloroformate,10, e.g. methyl chloroformate, is then added, again maintaining thetemperature between -10° and 10° C. The reaction is completed bystirring at room temperature or refluxing the reaction for a period ofone to 24 hours. The product Ia can be isolated as described above.

For amidrazones, which contain a reactive group on the benzene ring,e.g. bromine, cyano or nitro, the butyllithium method of Equation c isnot as desirable as the phosgene method described in Equation B.

The compounds of Formula Ib ##STR11## wherein Z is N--R' in Formula Iare prepared in a manner analogous to the preparation of compounds ofFormula Ia i.e. by either the phosgene-thiophosgene procedure (EquationB) or by the butyllithium procedure (Equation c). The requiredamidrazones 11 for the preparation of compounds with Formula Ib may beprepared ##STR12## by the imino ether route described above in EquationA. For compounds of Formula 11a wherein n is 2, 3, 4 and m is 0, theimino ether route is not very effective. In those cases the amidrazones11a should be prepared as shown in Equations D. and E. In ##STR13## InEquation D, R^(IV) X' is an alkylating agent wherein R^(IV) is a loweralkyl (C₁ -C₈) especially methyl or ethyl and X' is halide (e.g.iodide). Further details of this procedure can be found in the art, e.g.U.S. Pat. No. 3,480,030.

The compounds of Formula Ic, wherein Z is sulfur and Q is oxygen inFormula I ##STR14## can be prepared from amidrazones 18 by either thephosgene procedure or by the butyllithium-alkylchloroformate proceduredescribed earlier for the preparation of Compounds Ia.

The amidrazones 18 are best prepared by reaction of the iminothioethers19 in which R" ##STR15## is lower alkyl (C₁ -C₈) especially methyl orethyl with the appropriate arylhydrazine acid salts 2 (hydrochloride) ina manner similar to that described in Belgium Pat. Nos. 802446 and802447 (Equation F).

The required iminothioethers 19 may be prepared by methods known tothose skilled in the art. For example, F. Hamer and R. Rathbone, J.Chem. Soc. 243 (1943) describes the preparation of 20 which can be usedto prepare compounds of ##STR16## this invention in which n is 3 and mis 0 in Formula Ic.

When compounds Ic are treated with one equivalent of an oxidizing agentin an appropriate solvent, e.g., metachloroperbenzoic acid in methylenechloride or hydrogen peroxide in acetic acid compounds Id in which Z isSO (p=1) and Q is oxygen in Formula I are produced. (Scheme 1) ##STR17##

Treatment of Compounds Id with an equivalent of an oxidizing agentresults in the formation of Ie in which Z is SO₂ and Q is oxygen inFormula I. Compounds Ic are also prepared directly by reaction of Icwith two equivalents of an oxidizing agent as shown in Scheme 1. Thereaction of sulfides with oxidizing agents to produce sulfoxides andsulfones is well known in the art. For further details of this proceduresee the description by G. Hilgetag and A. Martin in "Preparative OrganicChemistry", Wiley, 1972 pp 667-669 and E. A. Fehnel and M. Carmack in J.Am. Chem. Soc. 70, 1813 (1948).

Compounds If in which Z is S(O)p and Q is sulfur in Formula I ##STR18##may be prepared by treatment of amides of Formula Ic, Id or Ie withreagents suitable for converting amides to thioamides e.g. phosphorouspentasulfide. Methods for converting amides to thioamides are well knownin the art. Details of this procedure may be found in article by D.Paquer in Int. J. Sulfur Chem., 8 (1), 173 (1973) and P. Weintraub ibid,8 (2), 321 (1973).

The following examples further illustrate the preparation of thecompounds of this invention. Unless otherwise indicated all parts are byweight and the temperatures in ° C.

EXAMPLE 1 Preparation of2[2,4-dichloro-5-(1-methylethoxy)phenyl]-6,7-dihydro-5H-1,2,4-triazolo[3,4-B][1,3]-oxazine-3(2H)-one

3.5 Parts of the hydrochloride salt of the2,4-dichloro-5-(1-methylethoxy)phenylhydrazone of3,4,5,6-tetrahydro-1,3-oxazin-2-one (prepared by methods similar tothose described in Belgian Pat. Nos. 802446 and 802447) were combinedwith 75 parts of dry tetrahydrofuran and cooled to -10° under anatmosphere of nitrogen. To this solution 27.1 parts of a solution of1.6M n-butyllithium in hexane, purchased from Foote Mineral Company,Exton, Pa., was added dropwise while maintaining the temperature of thereaction between -10° and +10°. The reaction mixture was stirred forabout 15 minutes following the addition of n-butyllithium. Then 1.0 partof methyl chloroformate was added dropwise while maintaining thetemperature between -10° and +10°. After the addition of thechloroformate was completed the cooling bath was removed and thereaction was allowed to warm to room temperature. It was then stirredfor about 30 minutes. The crude reaction mixture was poured into 500parts of water. The aqueous solution was then extracted 3 times with 200parts of methylene chloride. The crude extracts were combined and driedover anhydrous sodium sulfate and then filtered. The solvent was removedfrom the filtrate by evaporation under a reduced pressure of 50-300mm ona rotary evaporator. The crude product was purified by dry columnchromatography on alumina with chloroform; 0.6 parts of material with mp179.5-180.5 was obtained.

Using a procedure analogous to Example 1 and the appropriate amidrazoneor using the phosgene-thiophosgene procedure described earlier, thefollowing compounds of Formula Ia may be prepared (unless otherwisespecified "Properties" designates melting point in ° C.)

    ______________________________________                                        n   m     Y      X     V           Q   Properties                             ______________________________________                                        2   1     Cl     Cl    H           O   144-145                                2   1     Cl     Cl    OCH.sub.3   O   178-179                                2   1     Cl     Cl    OCH(CH.sub.3).sub.2                                                                       O   oil-IR bands:                                                                 1700cm.sup.-1,                                                                1580 cm.sup.-1.                        3   0     Cl     Cl    OCH.sub.3   O   122-123.5                                                                     oil-NMR                                3   0     Cl     Cl    H           O   (CDCl.sub.3)(δ)                                                         2.3 (m,2H),                                                                   4.0 (t,2H),                                                                   4.7 (t,2H),                                                                   7.9 (m,3H)                             3   0     F      Cl    H           O   116-118                                2   1     Cl     Cl    H           S                                          3   0     Cl     Cl    OCH.sub.3   O                                          1   2     Cl     Cl    OCH.sub.2 CH.sub.3                                                                        O                                          0   3     Cl     Cl    OCH(CH.sub.3).sub.2                                                                       O                                          4   0     Cl     Cl    O(CH.sub.2).sub.2 CH.sub.3                                                                O                                          0   4     Cl     Cl    O(CH.sub.2).sub.3 CH.sub.3                                                                O                                          2   1     Cl     Cl    OCH.sub.2 CH(CH.sub.3).sub. 2                                                             O                                          2   1     Cl     Cl    OCH(CH.sub.3)CH.sub.2 CH.sub.3                                                            O                                          2   1     F      F     F           O                                          1   2     Cl     Cl    Cl          O                                          1   2     Cl     Cl    Br          O                                          1   2     H      Cl    Cl          O                                          3   0     Br     Br    H           O                                          2   1     Cl     NO.sub.2                                                                            H           O                                          2   1     H      CN    H           O                                          2   1     H      H     H           O                                          2   1     CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3    O                                          2   1     CH.sub.3                                                                             OCH.sub.3                                                                           H           O                                          ______________________________________                                    

EXAMPLE 2 Preparation of2-(2,4-dichlorophenyl)-5,6,7,8-tetrahydro-8-methyl-1,2,4-triazolo[4,3-a]pyrimidin-3(2H)-one

10.3 Parts of the hydroiodide salt of3,4,5,6-tetrahydro-1-methyl-2(1H)-pyrimidinone(2,4-dichlorophenyl)hydrazone (prepared by methods similar to thosedescribed in U.S. Pat. No. 3,480,630) were added to 150 parts of drytetrahydrofuran. The mixture was cooled to -10° C. under an atmosphereof nitrogen. To this mixture was added dropwise 100 parts of a solutionof 1.6M n-butyllithium in hexane while maintaining the temperature ofthe reaction between 0° and -10°. After the addition was completed thereaction was stirred for five minutes. 4.0 parts of methylchloroformatewas added dropwise. The temperature was maintained at -10° during theaddition. After the addition was completed, the cooling bath wasremoved. The reaction was stirred for 30 minutes at ambient temperature.The crude reaction mixture was poured into 500 parts of water andconcentrated hydrochloric acid was added to the mixture to lower the pHto 7. The crude product was isolated by extraction of the aqueoussolution successively with three 200 part portions of methylenechloride. The crude extracts were combined and dried over anhydroussodium sulfate and then filtered. The solvent was removed from thefiltrate by evaporation under a reduced pressure of 50-300 mm on arotary evaporator. The crude product was purified by dry columnchromatography on alumina with 2% ethanol in chloroform. 0.7 parts ofproduct with mp 148°-152° was isolated.

Using a procedure analogous to Example 2 and the appropriate amidrazoneor using thiophosgene-phosgene procedure described earlier and theappropriate amidrazone the following compounds of Formula Ib may beprepared.

    __________________________________________________________________________    n m R'     Y  X   V         Q Properties                                      __________________________________________________________________________    3 0 CH.sub.3                                                                             H  Cl  H         O 218-222                                         3 0 CH.sub.3                                                                             H  H   H         O 80-83°                                   3 0 CH.sub.3                                                                             Cl Cl  OCH(CH.sub.3).sub.2                                                                     O oil-IR bands                                                                  1710 cm.sup.-1,                                                               1620 cm.sup.-1.                                 2 1 CH.sub.2 CH.sub.3                                                                    Cl Cl  H         S                                                 3 0 CH.sub.2 CH.sub.2 CH.sub.3                                                           Cl Cl  OCH.sub.3 O                                                 1 2 CH(CH.sub.3).sub.2                                                                   Cl Cl  OCH.sub.2 CH.sub.3                                                                      O                                                 0 3 CH.sub.3                                                                             Cl Cl  OCH(CH.sub.3).sub.3                                                                     O                                                 4 0 CH.sub.3                                                                             Cl Cl  O(CH.sub.2).sub.2 CH.sub.3                                                              O                                                 0 4 CH.sub.3                                                                             Cl Cl  O(CH.sub.2).sub.3 CH.sub.3                                                              O                                                 2 1 CH.sub.3                                                                             Cl Cl  OCH.sub.2 CH(CH.sub.3).sub.2                                2 1 CH.sub.3                                                                             Cl Cl  OCH(CH.sub.3)CH.sub.2 CH.sub.3                                                          O                                                 2 1 CH.sub.3                                                                             F  F   F         O                                                 1 2 CH.sub.3                                                                             Cl Cl  Cl        O                                                 1 2 CH.sub.3                                                                             Cl Cl  Br        O                                                 1 2 CH.sub.3                                                                             H  Cl  Cl        O                                                 3 0 CH.sub.3                                                                             Br Br  H         O                                                 2 1 CH.sub.3                                                                             Cl NO.sub.2                                                                          H         O                                                 2 1 CH.sub.3                                                                             H  CN  H         O                                                 2 1 CH.sub.3                                                                             H  H   H         O                                                 2 1 CH.sub.3                                                                             CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3  O                                                 2 1 CH.sub.3                                                                             CH.sub.3                                                                         OCH.sub.3                                                                         H         O                                                 __________________________________________________________________________

EXAMPLE 3 Preparation of2-(2,4-dichloro-5-methoxyphenyl)-2,5,6,8-tetrahydro-3H-1,2,4-triazolo[3,4-C] [1,4]-thiazine-3-thione A. Preparation of2,4,5,6-tetrahydro-1,4-thiazin-3-(4H)-one(2,4-dichloro-5-methoxyphenyl)hydrazone Fluorosulfate salt

3.2 parts of 2,4,5,6-tetrahydro-1,4-thiazin-3-(4H)thione (prepared bymethods taught in Chem. Abs. 70 12646y) was dissolved in 50 parts ofmethylene chloride. To this solution kept under an atmosphere ofnitrogen and cooled to 10° was added dropwise 2.8 parts of methylfluorosulfate. The temperature of the reaction was held at 10° duringthe addition. After the addition of methyl fluorosulfate was completed,the cooling bath was removed and the reaction mixture was allowed towarm to room temperature. 5.0 parts of 2,4-dichloro-5-methoxyphenylhydrazine was added to the reaction mixture. The reaction mixture wasstirred for one hour. The solid precipitate which formed was filteredand washed with 50 parts of diethyl ether. 7.4 parts of material with mp180°-188° was obtained.

B. Preparation of2-(2,4-dichloro-5-methoxyphenyl)-2,5,6,8-tetrahydro-3H-1,2,4-triazolo[3,4-C] [1,4]-thiazine-3-thione

3.7 parts of the fluorosulfate salt of2,4,5,6-tetrahydro-1,4-thiazin-3(4H)-one(2,4-dichloro-5-methoxyphenyl)hydrazone was added to 100 parts of drytetrahydrofuran containing 3.1 parts of triethylamine. To the abovemixture was added 1.3 parts of thiophosgene. The mixture was thenrefluxed for three hours. The crude reaction product which formed wasfiltered through alumina for dry column chromagtography (purchased fromICN Pharmaceuticals, Cleveland, Ohio). The solvent was evaporated fromthe filtrate at a reduced pressure of 50-300 mm on a rotary evaporator.The residue was crystallized from a mixture of toluene andmethylcyclohexane. 0.8 parts of product with mp 131°-135° was obtained.

By using a procedure analogous to Example 3 and the appropriateamidrazone and either phosgene or thiophosgene. The following compoundsof Formula I wherein Z is sulfur may be prepared.

    ______________________________________                                        n   m       Y        X       V             Q                                  ______________________________________                                        2   0       Cl       Cl      H             0                                  2   1       Cl       Cl      OCH.sub.3     O                                  3   0       Cl       Cl      OCH.sub.2 CH.sub.3                                                                          0                                  4   0       Cl       Cl      OCH(CH.sub.3).sub.2                                                                         0                                  1   2       Cl       Cl      O(CH.sub.2).sub.2 CH.sub.3                                                                  0                                  1   3       Cl       Cl      O(CH.sub.2).sub.3 CH.sub.3                                                                  0                                  3   0       Cl       Cl      OCH.sub.2 CH(CH.sub.3).sub.2                                                                O                                  3   0       Cl       Cl      OCH(CH.sub.3)CH.sub.2 CH.sub.3                                                              0                                  3   0       F        F       F             0                                  3   0       Cl       Cl      Cl            0                                  3   0       Cl       Cl      Br            0                                  3   0       H        Cl      Cl            0                                  3   0       Br       Br      H             0                                  2   1       Cl       NO.sub.2                                                                              H             0                                  3   0       H        CN      H             0                                  2   1       H        H       H             0                                  3   0       CH.sub.3 CH.sub.3                                                                              CH.sub.3      0                                  3   0       CH.sub.3 OCH.sub.3                                                                             H             0                                  ______________________________________                                    

Treatment of the compounds of Formula Ic (prepared as described inExample 3) with one equivalent of meta-chloroperbenzoic acid leads tocompounds having Formula Id. Treatment of the compounds of Formula Icwith two equivalent of meta-chloroperbenzoic acid leads to compounds offormula Ie. By this procedure the following compounds with Formula Id orIe may be prepared.

    ______________________________________                                        n    m      Y       X      V             Z                                    ______________________________________                                        2    1      Cl      Cl     OCH.sub.3     SO                                   3    0      Cl      Cl     OCH.sub.2 CH.sub.3                                                                          SO.sub.2                             4    0      Cl      Cl     OCH(CH.sub.3).sub.2                                                                         SO.sub.2                             1    2      Cl      Cl     O(CH.sub.2).sub.2 CH.sub.3                                                                  SO.sub.2                             1    3      Cl      Cl     O(CH.sub.2).sub.3 CH.sub.3                                                                  SO.sub.2                             3    0      Cl      Cl     OCH.sub.2 CH(CH.sub.3).sub.2                                                                SO.sub.2                             3    0      Cl      Cl     OCH(CH.sub.3)CH.sub.2 CH.sub.3                                                              SO.sub.2                             2    1      F       F      F             SO.sub.2                             2    1      Cl      Cl     Cl            SO.sub.2                             2    1      Cl      Cl     Br            SO.sub.2                             2    1      H       Cl     Cl            SO.sub.2                             2    1      Br      Br     H             SO.sub.2                             2    1      Cl      NO.sub.2                                                                             H             SO.sub.2                             2    1      H       CN     H             SO.sub.2                             2    1      H       H      H             SO.sub.2                             2    1      CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3      SO.sub.2                             2    1      CH.sub.3                                                                              CH.sub.3 O                                                                           H             SO.sub.2                             ______________________________________                                    

When the compounds of Formula Id and Ie are treated with an equivalentof phosphorous pentasulfide, the following compounds of Formula If inwhich p is o, 1 or 2 and Q is sulfur may be prepared.

    ______________________________________                                        n    m      Y       X      V             Z                                    ______________________________________                                        2    1      Cl      Cl     OCH.sub.3     SO                                   3    0      Cl      Cl     OCH.sub.2 CH.sub.3                                                                          S                                    4    0      Cl      Cl     OCH(CH.sub.3).sub.2                                                                         SO.sub.2                             1    2      Cl      Cl     O(CH.sub.2).sub.2 CH.sub.3                                                                  SO.sub.2                             1    3      Cl      Cl     O(CH.sub.2).sub.3 CH.sub.3                                                                  SO.sub.2                             3    0      Cl      Cl     O(CH.sub.2)CH(CH.sub.3).sub.2                                                               SO.sub.2                             3    0      Cl      Cl     OCH(CH.sub.3)CH.sub.2 CH.sub.3                                                              SO.sub.2                             2    1      F       F      F             SO.sub.2                             2    1      Cl      Cl     Cl            SO.sub.2                             2    1      Cl      Cl     Br            SO.sub.2                             2    1      H       Cl     Cl            SO.sub.2                             2    1      Br      Br     H             SO.sub.2                             2    1      Cl      NO.sub.2                                                                             H             SO.sub.2                             2    1      H       CN     H             SO.sub.2                             2    1      H       H      H             SO.sub.2                             2    1      CH.sub.3                                                                              CH.sub.3                                                                             CH.sub.3      SO.sub.2                             2    1      CH.sub.3                                                                              CH.sub.3 O                                                                           H             SO.sub.2                             ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I include dusts,granules, pellets, solutions, suspensions, emulsions, wettable powders,emulsifiable concentrates and the like. Many of these formulations canbe applied directly. Sprayable formulations can be extended in suitablemedia and used at spray volumes of from a few liters to several hundredliters per hectare. High strength formulations are used primarily forpreparing more dilute field strength formulations. The formulations,broadly, contain about 0.05% to 99% by weight of active ingredient(s)and at least one of (a) about 0.01 to 20% surfactant(s) and (b) about 1%to 99.95% solid or liquid diluent(s). More specifically, they willusually contain these ingredients in the following approximateproportions:

    ______________________________________                                                   Percent by Weight                                                             Active                                                                        Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                    ______________________________________                                        Wettable Powders                                                                           5-90       1-94     1-10                                         Oil Suspensions,                                                              Emulsions, Solutions                                                          (including Emulsifi-                                                          able Concentrates)                                                                         5-50      40-95     0-15                                         Aqueous Suspensions                                                                        5-50      40-94     1-20                                         Dusts        0.05-25     70-99.95                                                                              0-5                                          Granules and Pellets                                                                       0.05-95      1-99.95                                                                              0-15                                         High Strength                                                                 Compositions 90-99      1-10     0-2                                          ______________________________________                                    

Lower or higher levels of active ingredients can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook onInsecticide Dust Diluents and Carriers", 2nd. Edn., Dorland Books,Caldwell, N.J. Suitable diluents include finely divided or granularsolids classified as attapulgites, botanicals, calcites, diatomites,dolomites, gypsum, kaolinites, limestones, mica, montmorillonoids,phosphates, pyrophyllites, sulfur, sand, talcs, tripolites, vermiculite,and synthetics such as precipated, hydrated silicon dioxide, precipated,hydrated calcium silicate, precipated calcium carbonate and syntheticorganics. The more absorptive diluents are preferred for wettablepowders and the denser ones for dusts. Typical liquid diluents andsolvents are described in Marsden, "Solvents Guide", 2nd. Edn.,Interscience, New York, 1950. Solubility under 0.1% is preferred forsuspension concentrates; solution concentrates are preferably stableagainst phase separation at 0° C. "McCutcheon's Detergents andEmulsifiers 1975 Annual", MC Publ. Corp., Ridgewood, N.J., as well asSisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ.Col, New York, 1964, list surfactants and recommended uses. Allformulations can contain minor amounts of additives to reduce foaming,caking, corrosion, microbiological growth, etc., or to mark visually thearea that has been treated.

Solutions are prepared by simply mixing the ingredients. Fine solidcompositions are made by blending and, usually, grinding as in a hammeror fluid energy mill. Suspensions are prepared by wet milling (see, forexample, Littler, U.S. Pat. No. 3,060,084).

Granules may be made in several ways. For example, the active ingredientmay be sprayed onto preformed granular carriers. Suitable preformedgranular carriers include those suitable diluents listed earlier havinga particle size range from USS Sieve No. 200 (74 microns) to USS SieveNo. 10 (2000 microns). The preferred particle size is from USS Sieve No.140 (105 microns) to USS Sieve No. 20 (840 microns). Depending upon thenature of the carrier, the active ingredient may remain on the surfaceof the carrier or be absorbed into the carrier. Usually when the activeingredient remains on the surface of the carrier, a binding agent isused to hold the active ingredient on the surface. The binding agentshould bind the active ingredient to the surface well enough so that notmore than 10% of the active ingredient is removed during normal shippingand handling operations. Suitable binding agents include materials whichare at least partially soluble in any liquid used in the manufacture ofthe granules and which adhere to the granular surface. Water-solublebinders are preferred. Suitable binders include, but are not limited to,water-soluble polymers such as polyvinylalcohols, polyvinylpyrrolidones,polyoxyethylenes. Other suitable binders include, ligninsulfonates,starches, sugars, and certain surface active agents listed in"McCutcheons' Detergents and Emulsifiers 1975 Annual", MC Publ. Corp.,Ridgewood, N.J.

The active ingredient may be sprayed onto the granules as a solution ina suitable solvent, which may or may not be removed from theformulation. If the active ingredient is a liquid, it may be sprayedonto or mixed with the carrier directly. If it is a solid, it may bemelted and applied directly as a liquid. If very low strength granulesare desired, the active ingredient may be vaporized onto the carrier.Granules may also be prepared by agglomeration techniques. For example,the active ingredient and a finely divided solid diluent may be mixedand agglomerated by techniques known in the art, such as by sprayingwith a liquid in a fluidized bed or pan granulator. The activeingredient and diluent may also be mixed with other formulationingredients and pelletized. The pellets may then be crushed to a desiredgranular size. Pellets may be made by agglomeration techniques. See J.E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp.147ff. and "Perry's Chemical Engineer's Handbook", 4th Edn.,McGraw-Hill, N.Y., 1963, pp. 8-59ff.

For further information regarding the art of formulation, see forexample:

H. m. loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, Line 16through Col. 7, Line 19 and Examples 10 through 41.

R. w. luckenbaugh, U.S. Pat. No. 3,309,192, March 14, 1967, Col. 5, Line43 through Col. 7, Line 62, and Ex. 8, 12, 15, 39, 41, 52, 53, 58, 132,138-140, 162-164, 166, 167, 169-182.

H. gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,Line 66 through Col. 5, Line 17 and Examples 1-4.

G. c. klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961 pp. 81-96.

J. d. fryer and S. A. Evans, "Weed Control Handbook", 5th Edn. BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

EXAMPLE 3

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-6,7-dihydro-5H-1,2,4-                                                 triazolo[3,4-B][1,3]oxazin-3(2H)-one                                                                 25%                                                    Sodium ligninsulfonate                                                                              2%                                                      Sodium alkylnaphthalene sulfonate                                                                   2%                                                      Synthetic amorphous silica                                                                          3%                                                      Kaolinite              68%                                                    ______________________________________                                    

The ingredients are blended thoroughly, ground in an air mill to producean average particle size under 15 microns, reblended and sifted througha U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

EXAMPLE 4

    ______________________________________                                        Solution                                                                      ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-5,6,7,8-tetrahydro-8-methyl-                                          1,2,4-triazolo[4,3-A]pyrimidin-3(2H)-                                         one                   20%                                                     Dimethylformamide     80%                                                     ______________________________________                                    

The ingredients are combined and stirred to produce a solution, whichcan be used for low-volume applications.

EXAMPLE 5

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        2-(2,4-dichloro-5-methoxyphenyl)-6,-                                          7-dihydro-5H-1,2,4-triazolo[3,4-B]-                                           [1,3]oxazin-3(2H)-one 1%                                                      Anhydrous sodium sulfate                                                                             10%                                                    Crude Calcium ligninsulfonate                                                                       5%                                                      Sodium alkylnaphthalenesulfonate                                                                    1%                                                      Polyoxyethylene (4 × 10.sup.6 average                                   molecular weight)     1%                                                      Calcium/magnesium bentonite                                                                          82%                                                    ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 6

    ______________________________________                                        Emulsifiable Concentrate                                                      ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-2,5,6,8-tetrahydro-3H-1,-                                             2,4-triazolo[3,4-C][1,4]oxazin-3-one                                                                  25%                                                   Blend of oil soluble sulfonates and                                           polyoxyethylene ethers   4%                                                   Xylene                  71%                                                   ______________________________________                                    

The ingredients are combined and stirred until solution is complete. Afine screen filter is included in packaging operation to insure theabsence of any extraneous undissolved material in the product.

EXAMPLE 7

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-6,7-dihydro-5H-1,2,4-triazolo-                                        [3,4-B][1,3]oxazin-3(2H)-one                                                                         50.0%                                                  Polyacrylic acid thickener                                                                           0.3%                                                   Dodecylphenol polyethylene                                                    glycol ether           0.5%                                                   Disodium phosphate     1.0%                                                   Monosodium phosphate   0.5%                                                   Polyvinylalcohol       1.0%                                                   Pentachlorophenol      0.4%                                                   Water                  46.3%                                                  ______________________________________                                    

The ingredients are ground together in a sand mill to produce particlesessentially all under 5 microns in size.

EXAMPLE 8

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        2-(2,4-dichloro-5-methoxyphenyl)-                                             6,7-dihydro-5H-1,2,4-triazolo[3,4-                                            B][1,3]oxazin-3(2H)-one                                                                              50%                                                    Sodium alkylnaphthalenesulfonate                                                                    2%                                                      Sodium ligninsulfonate                                                                              2%                                                      Synthetic amorphous silica                                                                          3%                                                      Kaolinite              43%                                                    ______________________________________                                    

The ingredients are thoroughly blended, passed through an air mill toproduce an average particle size under 15 microns, reblended, and siftedthrough a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

EXAMPLE 9

    ______________________________________                                        High-Strength Concentrate                                                     ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-6,7-dihydro-5H-1,2,4-triazolo-                                        [3,4-B][1,3]oxazin-3(2H)-one                                                                          99%                                                   Trimethylnonyl polyethylene                                                   glycol ether             1%                                                   ______________________________________                                    

The surfactant is sprayed on the active ingredient in a blender and themixture sifted through a U.S.S. No. 40 sieve (0.42 mm openings) prior topackaging. The concentrate may be formulated further for field use.

EXAMPLE 10

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-5,6,7,8-tetrahydro-8-methyl-                                          1,2,4-triazolo[4,3-A]pyrimidin-3-                                             (2H)-one                  0.5%                                                Attapulgite granules (low volatile                                            matter; 0.59-0.25 mm., i.e. USS 30-                                           60 mesh size)            99.5%                                                ______________________________________                                    

Forty grams of a solution containing 2.5%2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-5,6,7,8-tetrahydro-8-methyl-1,2,4-triazolo[4,3-A]pyrimidin-3(2H)-onedissolved in methyl alcohol are slowly atomized onto a fluidized bed ofattapulgite granules (199 gm). Fluidization of the granules is continuedafter atomization is complete and until all the methyl alcohol isevaporated from the granules. The granules are packaged for use.

EXAMPLE 11

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        2-(2,4-dichloro-5-methoxyphenyl)-6,7-                                         dihydro-5H-1,2,4-triazolo[3,4-B][1,3]-                                        oxazin-3(2H)-one         25%                                                  Anhydrous sodium sulfate 10%                                                  Crude Calcium ligninsulfonate                                                                           5%                                                  Sodium alkylnaphthalenesulfonate                                                                        1%                                                  Calcium/magnesium bentonite                                                                            59%                                                  ______________________________________                                    

The ingredients are blended, hammer milled and moistened with about10-12% water. The mixture is then extruded as cylinders about 3 mm indiameter which are cut to be about 3 mm long. These pellets may be useddirectly after drying or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm opening). The pellets retained on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 12

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-6,7-dihydro-5H-1,2,4-                                                 triazolo[3,4-B][1,3]oxazin-3(2H)-one                                                                    0.2%                                                Anhydrous sodium sulfate 10%                                                  Crude Calcium ligninsulfonate                                                                          5%                                                   Sodium alkylnaphthalenesulfonate                                                                       1%                                                   Finely divided attapulgite clay                                                                        83.8%                                                ______________________________________                                    

The ingredients are blended, hammer milled and placed in a fluidized bedgranulator. Water is aspirated into the fluidized bed of powder untilsmall granules are formed. Water aspiration is then stopped butfluidization is continued to dry the formed ganules. The granules areremoved from the granulator and screened to pass a U.S.S. No. 20 sieve(0.84 mm opening). Granules retained on a U.S.S. No. 40 sieve (0.42 mmopening) are packaged for use. Granules larger than 0.84 mm are groundand recycled. Fines smaller than 0.42 mm are also recycled.

EXAMPLE 13

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        2-(2,4-dichloro-5-methoxyphenyl)-6,7-                                         dihydro-5H-1,2,4-triazolo[3,4-B]-                                             [1,3]oxazin-3(2H)-one    0.1%                                                 Anhydrous sodium sulfate                                                                              10%                                                   Crude Calcium ligninsulfonate                                                                         5%                                                    Sodium alkylnaphthalenesulfonate                                                                      1%                                                    Polyoxyethylene (4 × 10.sup.6 average                                   molecular weight)       1%                                                    Calcium/magnesium bentonite                                                                           82.9%                                                 ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about12% water. The moist mixture is extruded as cylinders about 1 mm indiameter and about 2 mm long. These small pellets are dried andpackaged. They are applied directly.

EXAMPLE 14

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-2,5,6,8-tetrahydro-3H-                                                1,2,4-triazolo[3,4-C][1,4]oxazin-3-one                                                                  0.05%                                               Dimethylformamide        5%                                                   Attapulgite granules (low volatile                                            matter; 0.59-0.25 mm i.e. U.S.S. No.                                          30-60 mesh size)         94.95                                                ______________________________________                                    

One-tenth of a gram of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-2,5,6,8-tetrahydro-3H-1,2,4-triazolo[3,4-C][1,4]oxazin-3-oneis dissolved in 9.9 grams of dimethylformamide. This solution is veryslowly atomized onto 190.1 grams of a rapidly tumbling bed of theattapulgite granules. After application of the active is complete, theformulation is blended for a few additional minutes. Thedimethylformamide is not removed from the formulation. The granules arepackaged for use.

EXAMPLE 15

    ______________________________________                                        Emulsifiable Concentrate                                                      ______________________________________                                        2-[2,4-dichloro-5-(1-methylethoxy)-                                           phenyl]-5,6,7,8-tetrahydro-8-methyl-                                          1,2,4-triazolo[4,3-A]pyrimidin-3(2H)-one                                                                10%                                                 Blend of oil-soluble sulfonate with                                           polyoxyethylene ethers     6%                                                 Aromatic hydrocarbon solvent with a                                           Tag closed cup flash point between                                            100 and 115° F.    84%                                                 ______________________________________                                    

The ingredients are combined and stirred until solution is complete. Thesolution is filtered through a fine screen filter prior to packaging toremove any extraneous undissolved material.

EXAMPLE 16

    ______________________________________                                        Low Strength Granules                                                         ______________________________________                                        2-(2,4-dichloro-5-methoxyphenyl)-                                             6,7-dihydro-5H-1,2,4-triazolo[3,4-B]-                                         [1,3]oxazin-3(2H)-one     0.1%                                                Sodium ligninsulfonate   5%                                                   Preformed sand granules having a                                              particle size distribution from -U.S.S. sieve No. 140 (150 microns)           to U.S.S. sieve No. 50 (297 microns)                                                                   94.9%                                                ______________________________________                                    

0.5 Gram2-(2,4-dichloro-5-methoxyphenyl)-6,7-dihydro-5H-1,2,4-triazolo[3,4-B][1,3]-oxazin-3(2H)-oneand 25 gm sodium ligninsulfonate are dissolved in 50 gm water. Thissolution is slowly sprayed onto a tumbling bed of the sand granules(474.5 g). After spraying is complete, the tumbling granules are warmedto remove the water. The resulting granules are packaged for use.

The compounds of Formula I may be formulated using the proceduresoutlined in Examples 3-16.

UTILITY

The compounds of the present invention are useful when applied as pre-and/or post-emergence treatments for broad-spectrum control of a widevariety of weed and brush species growing on industrial sites, storagelots, along fences and building foundations, along railroad and utilityrights-of-way, prison perimeter security patrol corridors, etc.

The precise amount of the compounds of the invention to be used in anyparticular situation will vary widely according to the end resultdesired. Factors affecting the optimum rate of application include theplant species to be controlled, soil type, formulation used, prevailingweather conditions, foliage density, length of time for which residualactivity is desired, etc. Broadly speaking, the compounds are used atlevels of about 0.25 to 20 kilograms per hectare, preferablyapproximately 0.50 to 10 kilograms per hectare. In general, the higherrates of application from within this range will be selected for adverseconditions or where extended persistence in soil is desired.

Herbicidal activity of the subject compounds was discovered in a numberof greenhouse tests. Test procedures are described below.

Test A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), Cassia tora, morningglory (Ipomoeaspp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, wheatand nutsedge tubers were planted in a growth medium and treatedpreemergence with the chemicals dissolved in a non-phytotoxic solvent.At the same time, cotton having five leaves (including cotyledonaryones), bush beans with the third trifoliolate leaf expanding, crabgrasswith two leaves, barnyardgrass with two leaves, wild oats with one leaf,cassia with three leaves (including cotyledonary ones), morningglorywith four leaves (including the cotyledonary ones), cocklebur with fourleaves (including the cotyledonary ones), sorghum with three leaves,corn with three leaves, soybean with two cotylegonary leaves, rice withtwo leaves, wheat with one leaf, and nutsedge with three-five leaveswere sprayed. Treated plants and controls were maintained in agreenhouse for sixteen days, whereupon all species were compared tocontrols and visually rated for response to treatment. The ratings arebased on a numerical scale extending from 0 = no injury, to 10 =complete kill. The accompanying descriptive symbols have the followingmeanings:

B = burn; G = growth retardation; C = chlorosis/necrosis; D =defoliation; E = emergence inhibition; and H = formative effects. 6Yindicates abscised flower buds. The ratings for the compounds tested bythis procedure are shown in Table 1.

    TABLE 1       POST EMERGENCE         Barn-         Bush  Morning Cockle-   Crab-     yard COMPOUND KG/HA bean Cotton Glorybur Cassia Nutsedge grass grass     Wild oats Wheat Corn Soybean Rice Sorghum      ##STR19##      2/5 6B 6B 1B 2B 1B 1B 1B6C 3B 1B 1B 3B 2B 4B 4B      ##STR20##      2/5 3B6Y 9B 10B 5B 4D 3B 9B 6B 3B 3B 7B 7B 5B 8B      ##STR21##      22/5 9B9B 9B9B 10B8B 7B6B 9B5B 5B3B 9B9B 10B8B 8B5B 8B4G 7B6B 8B8B 8B7B 9     B7B      ##STR22##      2/5 7B 7B 2B 1B 1B 1B 2G 4B 2B 1B 2B 3B 3B 5B      ##STR23##     2/5 5B4H 9B 8B 5B 3B 3B 3B7H 6B 2B 4B 6B 6B 6B 7B      ##STR24##     2/5 9D 10B 8B 3B 2B 3B6C 3B8H 9B 4B 3B 5B 7B 8B 5B      ##STR25##      22/5 4B3B 5B4B 3B1B 1B1B 1B1B 00 2B1B 2D2B 1B1B 1B1B 1B1B 2B1B 1B1B     4B1B      ##STR26##      22/5 9B7B 9B7B 9B7B 3B3B 4B3B 2B5C1B 8B3B 9B5B8H 3B5H5B8H 3B6H2B 3B6C3B 9     B4B 10C3B 3B6C3B      ##STR27##      22/5 9B9B 9B9B 10B9B 9B8B 2B4H3B 5B8C2B6C 10B8B 10B10B 9B8B 9B7B 9B8B   9     9BB 9B8B 9B9B      ##STR28##      2 9B 10B 10B 9B 10B 10B 10B 10B 9B 9B 9B 9B 10B 9B      ##STR29##      22/5 9B8B 8B8B 9B5B 6B2B 6B4B 8B1B 10B9B 10B7B 9B3B 7B3B 9B7B  9B8B     8B4B 9B6B      ##STR30##      22/5 9B9B 9B8B7D 10B10B 6B3B 4B7H8B 5B9C 10B10B 10B10B 9B9B 9B5B     5B9H5B9H 9B9B 10B8B 9B9B        PRE-EMERGENCE   Morn-     Barn-        KG/ ing Cockle-  Nut- Crab     yard Wild   Soy  Sor- COMPOUND HA glory bur Cassia sedge grass grass     oats Wheat Corn bean Rice ghum      ##STR31##      2/5 0 0 1C 0 9C 9C 9C 9C 1C7H 1C 7C 2C9H      ##STR32##      2/5 10C 10E 10C 0 10C 9C 9C 7C 2C3H 1C 4C 2CTH      ##STR33##      22/5 10C2C8H 10C9C 10C10C 9C6C 10C10C 10C10C 10C10C 10C9C 9C9C 9H 1C5H     10C9C 10C9C      ##STR34##      2/5 6C 1C 9C 0 10E 9C 8C 9C 9C 2C 7C 10C      ##STR35##      2/5 2C7H 6G 2C7G 4C 10C 10C 9C 10C 9C 1C7G 9C 10C      ##STR36##      2/5 2C7H 6G 2C7G 4C 10C 10C 9C 10C 9C 1C7G 9C 10C      ##STR37##      22/5 2C0 00 00 10E3G 9H1C 9C0 3C8H0 1C0 1C0 1C-- 00 2C0      ##STR38##      22/5 10C10C 9C5C 10C10C 9C9G 10C10C 10C10C 9C9C 10C10C 10H10H 9H9H      7      9C2CG 10C9H      ##STR39##      22/5 10E1C9H 9C1C3H 10C5G 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C     9H9H 9C9C 10C10C      ##STR40##      2 10C 10C 10C 10C 10C 10C 10C 9C 10C 10C 10C 10C      ##STR41##      22/5 10C1C7G 10C10C 10C10C 10C8C 10C10C 10C10C 10C9C 10C10C 10H10H     10H9H 10C9C 10C10C      ##STR42##      22/5 10C10C 10C9C 10C10C 10C10C 10C10C 10C10C 10C10C 10C10C 10H10H     10H9H 10C9C 10C10C

Test B

Two 25-cm plastic bulb pans were filled with fertilized and limedFallsington silt loam. One pan was planted with corn, sorghum andseveral grassy weeds. The other pan was planted with soybeans, purplenutsedge (Cyperus rotundus), and several broadleaf weeds. The followinggrassy and broadleaf weeds were planted: crabgrass (Digitarissanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avenafatua), johnsongrass (Sorghum halepense), giant foxtail (Setariafaberii), Kentucky bluegrass (Poa pratensis), cheatgrass (Bromussecalinus), dallisgrass (Paspalum dilatatum), mustard (Brassicaarvensis), cocklebur (Xanthium pennsylvanicum), pigweed (Amaranthusretroflexus), morningglory (Ipomoea hederacea), cassia (Cassia tora),teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), andjimsonweed (Datura stramonium). A 12-cm diameter paper pot was alsofilled with prepared soil and planted with rice and wheat. Another 12-cmpot was planted with sugarbeets. The above four containers were treatedpreemergence (compound sprayed on soil surface before seed germination).

Twenty-eight days after treatment, the plants were visually rated usingthe same system as described above for Test A. The data are given inTable II.

                                      TABLE II                                    __________________________________________________________________________    FALLSINGTON SILT LOAM                                                                                 Barn-      John-   Giant                                                                             Ky.                                            Rate,                                                                             Crab-                                                                             yard-                                                                             Sor-                                                                              Wild                                                                             son-                                                                              Dallis-                                                                           fox-                                                                              blue-                                                                            Cheat-   Mus-                               kg/ha                                                                             grass                                                                             grass                                                                             ghum                                                                              oats                                                                             grass                                                                             grass                                                                             tail                                                                              grass                                                                            grass                                                                              Corn                                                                              tard               __________________________________________________________________________     ##STR43##      0.125 0.50                                                                        3H 10H                                                                            2H 10H                                                                            0 5H                                                                              0 6H                                                                             0 8H                                                                              2H 9H                                                                             0 10H                                                                             0 9H                                                                             0 3H 0 5H                                                                              6H 10H              ##STR44##      0.125  0.50                                                                       0 8H                                                                              0 3H                                                                              0 4H                                                                              0 2G                                                                             0 6H                                                                              0 3H                                                                              0 5H                                                                              0 2H                                                                             0 3H 0 0 0 8H                ##STR45##      0.063 0.125                                                                       0 9C                                                                              0 2C                                                                              0 0 0 0                                                                              0 0 0 9C                                                                              0 3C                                                                              0 0                                                                              0 0  0 0 2C 2C                              0.50                                                                              10C 8C  7C  3C 8C  10C 10C 8C 2C   4H  8C                  ##STR46##      0.063 0.125                                                                       8C 9C                                                                             7C 8C                                                                             3C 4C                                                                             0 5C                                                                             8C 6C                                                                             9C 10C                                                                            6C 10C                                                                            0 3C                                                                             0 0  0 0 7C 7C                              0.50                                                                              10C 10C 10C 9C 10C 10C 10C 10C                                                                              4C   6H  10C                __________________________________________________________________________                                   H.                                                                 Cock-      in-                                                                             Morn-     Vel-                                                                             Jim-                                            Rate,                                                                             le- Pig-                                                                             Nut-                                                                              di-                                                                             ing-                                                                              Cas-                                                                             Tea-                                                                             vet-                                                                             son-                                                                             Soy-      Sugar-                             kg/ha                                                                             bur weed                                                                             sedge                                                                             go                                                                              glory                                                                             sia                                                                              weed                                                                             leaf                                                                             weed                                                                             bean                                                                             Rice                                                                             Wheat                                                                             beets              __________________________________________________________________________     ##STR47##      0.125  0.50                                                                       0 0 0 10H                                                                            0 0 -- --                                                                           0 6H                                                                              0 9H                                                                             8H 10H                                                                           9H 10E                                                                           7H 10H                                                                           0 0                                                                              0 5H                                                                             0 3H                                                                              0 3H                ##STR48##      0.125 0.50                                                                        0 0 0 10E                                                                            0 0 -- --                                                                           0 3H                                                                              0 8H                                                                             0 3H                                                                             0 8H                                                                             0 2G                                                                             0 0                                                                              0 0                                                                              0 0 0 7H                ##STR49##      0.063 0.125                                                                       0 --                                                                              0 10C                                                                            0 0 -- --                                                                           0 0 -- --                                                                            -- --                                                                            -- --                                                                            4C 9C                                                                            0 0                                                                              0 2C                                                                             0 0 0 4G                               0.50                                                                              0   10C                                                                              2C  --                                                                              6C  -- -- -- 10C                                                                              2C 7C 4C  10C                 ##STR50##      0.063 0.125                                                                       0 --                                                                              3C 10C                                                                           0 0 -- --                                                                           0 2G                                                                              -- --                                                                            -- --                                                                            -- --                                                                            10C  10C                                                                         0 --                                                                             0 4C                                                                             0 0 0 2G                               0.50                                                                              --  10C                                                                              4G  --                                                                              8C  -- -- -- 10C                                                                              0  9C 3C  10C                __________________________________________________________________________

test C

25-cm diameter, plastic pots filled with Fallsington silt loam wereplant to soybeans, cotton, alfalfa, corn, rice, wheat, sorghum,velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), cassis(Cassia tora), morningglory (Ipomoea spp.), jimsonweed (Daturastramonium), cocklebur (Xanthium pennsylvanicum), crabgrass (Digitariaspp.), nutsedge (Cyperus rotundus), barnyardgrass (Echinochloacrusgalli), giant foxtail (Setaria faberi) and wild oats (Avena fatua).Eighteen days after planting, the young plants and the soil around themwere sprayed overall with the test chemical dissolved in anon-phytotoxic solvent. Fourteen days after treatment, all species werecompared to untreated controls and visually rated for response totreatment, again using the above-described scale.

The accordingly obtained data are presented in Table III.

                                      TABLE III                                   __________________________________________________________________________                            Over-the Top Soil/Foliage Treatment                                       Rate,                                                                             Soy-                                                                              Velvet-                                                                            Ses-       Morning- Jimson-                                                                            Cockle-                                 kg/ha                                                                             beans                                                                             leaf bania                                                                            Cassia                                                                            Cotton                                                                            glory                                                                              Alfalfa                                                                           weed bur                 __________________________________________________________________________     ##STR51##          0.125 0.50                                                                        3B 5B                                                                             9B --                                                                              5B 8B                                                                            2B 8B                                                                             6B 10B                                                                            3B 5B                                                                              2B 6B                                                                             3B 8B                                                                              -- --                ##STR52##          0.125 0.50                                                                        5B 5B                                                                             9B --                                                                              8B 8B 4B                                                                             10B 10B                                                                           8B 9B                                                                              4B 5B                                                                             9B 10B                                                                             -- --                ##STR53##          0.063 0.125 0.50                                                                  2B 3B 3B                                                                          -- -- 10B                                                                          2B 5B 8B                                                                         0 3B 4B                                                                           9B 10B 10B                                                                        2B 4B 6B                                                                           2B 4B 6B                                                                          10B 10B 10B                                                                        -- 2C 2B             ##STR54##          0.063  0.125 0.50                                                                 3B 5B 6B                                                                          4B -- 10B                                                                          5B -- --                                                                         2B 7B 10B                                                                         10B 10B 10B                                                                       4B 6B 10B                                                                          -- 6B 6B                                                                          8B 10B 10B                                                                         1C 3C 3B             ##STR55##          0.063 0.125 0.50                                                                  3B 4B 4B                                                                          10B 8B 10B                                                                         3B 3B 5B                                                                         2B 2B 4B                                                                          9B 9B 9B                                                                          4B 4B 6B                                                                           2B 2B 6B                                                                          4B 8B 9B                                                                           3B 3B 4B                                Rate,  Crab-         Barnyard- Giant                                                                              Wild                                      kg/ha                                                                             Corn                                                                             grass Rice                                                                             Nutsedge                                                                           grass Wheat                                                                             Foxtail                                                                           Oats                                                                             Sorghum             __________________________________________________________________________     ##STR56##          0.125 0.50                                                                        2B 4B                                                                            3B 5B 0 3B                                                                             0 0  2B 3B 0 2C                                                                              2C 4C                                                                             0 2C                                                                             3B 3B                ##STR57##          0.125 0.50                                                                        2B 4B                                                                            3B 6B 3B 5B                                                                            0 0  4B 6B 2B 3B                                                                             3B 7B                                                                             4B 5B                                                                            3B 3B                ##STR58##          0.063 0.125 0.50                                                                  1B 2B 2B                                                                         0 2C 0                                                                              2C 3C 5C                                                                         0 0 0                                                                              0 2B 4B                                                                             0 2C 3B                                                                           2B 4B 8B                                                                          0 0 4B                                                                           2B 4B 4B             ##STR59##          0.063 0.125 0.50                                                                  2B 2B 2B                                                                         2B 3B 6B                                                                            0 3B 6B                                                                          0 0 2C                                                                             3B 4B 7B                                                                            2B  2B 4B                                                                         3B 5B 7B                                                                          2B 3B 5B                                                                         2B 4B 7B             ##STR60##          0.063 0.125 0.50                                                                  2B 3B 7B                                                                         3C 3C 6C                                                                            3C 2C 6C                                                                         2C 2C &C                                                                           3C 5C 9C                                                                            2C 5C 6C                                                                          7C 8C 9C                                                                          2C 3C 6C                                                                         3C 4C 9C            __________________________________________________________________________

what is claimed is:
 1. A compound of the formula ##STR61## where V ishydrogen, fluorine, chlorine, bromine, methyl or OR where R is alkyl of1-4 carbon atoms;X is hydrogen, fluorine, chlorine, bromine, cyano,methyl, methoxy, or nitro; Y is hydrogen, fluorine, chlorine, bromine,or methyl; n, m is 0, 1, 2, 3 or 4; Q is oxygen or sulfur; Z is oxygen;p is 0, 1 or 2 and R' is alkyl of 1-3 carbon atomswith the provisos that(1) n + m = 2, 3, or 4; and (2) if n + m = 2 or 4 then Y, X ≠ H.
 2. Acompound of claim 1 wherein Q is oxygen.
 3. A compound of claim 1whereinV is hydrogen, chlorine, bromine or OR; X is fluorine, chlorineor bromine; Y is fluorine, chlorine, bromine, or methyl; and n + m is 3.4. A compound of claim 1 whereinV is hydrogen, chlorine or OR; X ischlorine or bromine; Y is fluorine, chlorine or bromine; and n + is 3.5. A compound of claim 1,2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-2,5,6,8-tetrahydro-3H-1,2,4-triazolo[3,4-C][1,4]-oxazin-3-one.6. A composition for the control of undesirable vegetation consistingessentially of a compound of claim 1 and at least one of (a) asurface-active agent, and (b) a solid or liquid diluent.
 7. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 2 and at least one of (a) asurface-active agent, and (b) a solid or liquid diluent.
 8. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 3 and at least one of (a) asurface-active agent, and (b) a solid or liquid diluent.
 9. Acomposition for the control of undesirable vegetation consistingessentially of a compound of claim 4 and at least one of (a) asurface-active agent, and (b) a solid or liquid diluent.
 10. Acomposition for the control of undesirable vegetation consistingessentially of the compound of claim 5 and at least one of (a) asurfact-active agent, and (b) a solid or liquid diluent.
 11. A methodfor the control of undesirable vegetation comprising applying to thelocus of such undesirable vegetation a herbicidally effective amount ofa compound of claim
 1. 12. A method for the control of undesirablevegetation comprising applying to the locus of such undesirablevegetation a herbicidally effective amount of a compound of claim
 2. 13.A method for the control of undesirable vegetation comprising applyingto the locus of such undesirable vegetation a herbicidally effectiveamount of a compound of claim
 3. 14. A method for the control ofundesirable vegetation comprising applying to the locus of suchundesirable vegetation a herbicidally effective amount of a compound ofclaim
 4. 15. A method for the control of undesirable vegetationcomprising applying to the locus of such undesirable vegetation aherbicidally effective amount of the compound of claim 5.